Journal of Organic Chemistry p. 4162 - 4167 (1980)
Update date:2022-08-05
Topics:
Sekine, Mitsuo
Satoh, Masaki
Yamagata, Hikaru
Hata, Tsujiaki
Studies on the benzoylation of amines of dialkyl benzoylphosphonates (1A-F) were described in detail. Stoichiometric reactions of diethyl benzoylphosphonate (1B) with a variety of amines (2a-i) gave amides as the main products along with diethyl phosphonate (4B) and α-(phosphoryloxy)benzyl phosphonate (5B). The yields of amides increased with the ratio of 1B/2a-i. The use of hindered dialkyl benzoylphosphonates resulted in high yields of amides while the reaction rates decreased markedly. The benzoylations of n-propylamine (2d) with 1B in various solvents having dielectric constants of 1.9-36.7 were conducted. The yields of N-n-propylbenzamide (3d) and 5B were surprisingly almost constant. However, the reaction rates varied as follows. In nonpolar solvents such as n-hexane and cyclohexane benzoylation was remarkably rapid while the benzoylation in methylene chloride was much slower than that in other solvents used. Compound 1B underwent smooth reaction with aliphatic amines but did not react with aromatic amines under the same conditions. Selective N-benzoylation of the bifunctional amine, ethanolamine, was achieved by means of diisopropyl benzoylphosphonate (1C) in tetrahydrofuran. The use of the hindered dialkyl benzoylphosphonate 1C resulted in poorer yields of amides in the case of the reaction with a hindered amine such as diethylamine, but higher yields of amides in the case of primary amines. Addition of triethylamine and 4-(dimethylamino)pyridine (DMAP) slightly accelerated the benzoylation, but yields of amides were similar to those in the absence of the catalysts. Optimum conditions for high yields of amides were proposed for the practical use of dialkyl benzoylphosphonates as the acylating agents in the present reaction.
View MoreHenan Yellow River New Material Technology Co.Ltd.
website:http://www.yellowriverchem.com
Contact:0086-373-7278760
Address:Chengguan Town, Yuanyang County
Contact:+86-371-55981030
Address:Room 1571, Macalline Soho, No.1, Shangdu Road, Zhengzhou, Henan
Jiangsu Chiatai Qingjiang Pharmaceutical Co.,Ltd
Contact:+86-517-86283327
Address:9 North Hantai Road, Huaian, China
Yuan Shi(SuQian)Biotechnology Co.,Ltd
website:http://www.yuanshibio.com
Contact:+86-527-84226672
Address:jiangsu suqian
NINGBO YINZHOU PRECISE COLOR CO.,LTD.
Contact:86-574-88139809 86-574-83033159
Address:Qiming Road,Yinzhou,Ningbo,China
Doi:10.1016/0040-4020(82)80188-9
(1982)Doi:10.1002/ardp.19833160309
(1983)Doi:10.1021/ja01175a062
(1949)Doi:10.1139/v61-338
(1961)Doi:10.1016/S0040-4039(00)61936-6
(1985)Doi:10.1002/jhet.5570130340
(1976)